In color photographic light-sensitive materials, dyes of yellow, magenta and cyan formed from couplers do not necessarily have ideal absorption characteristics. For example, it is normal that a magenta dye image absorbs more or less blue light in addition to the necessary absorption of green light, causing distortion in color reproducibility. In order to eliminate the above-mentioned distortion of color reproducibility, couplers colored with yellow or magenta are used before conducting coupling reaction with the oxidation product of aromatic primary amine color developer. The former coupler is so-called a colored magenta coupler and the latter coupler is so-called a colored cyan coupler.
The above-mentioned Auto-masking method employing colored couplers has been described in detail in J. Phot. Soc. Am., 13,94 (1947), J. Opt. Soc. Am., 40,166 (1950) or J. Am. Chem. Soc., 72,1533 (1950).
As colored magenta couplers having a main absorption in blue light area, 1-phenyl-3-acylamino-4-phenylazo-5-pyrazolone is described in U.S. Pat. Nos. 2,428,054 and 2,449,966, those having 4-methoxyarylazo group are described in U.S. Pat. No. 2,763,552, 1-phenyl-3-anilino-4-phenylazo-5-pyrazolone is described in U.S. Pat. No. 2,983,608, those having a naphthylazo group are described in U.S. Pat. Nos. 3,519,429 and 3,615,506, those having a water-soluble group are described in U.S. Pat. No. 1,044,778, those having a hydroxyphenylazo group are described in U.S. Pat. No. 3,476,564 and Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 123625/1974, 131448/1974 and 52532/1979, those having acylaminophenylazo group were described in Japanese Patent O.P.I. Publication No. 42121/1977, those having a substituted alkoxyphenylazo group are described in Japanese Patent O.P.I. Publication No. 102723/1977 and those having a thiophenylazo group are described in Japanese Patent O.P.I. Publication No. 63016/1978.
However, the above-mentioned colored magenta couplers are not satisfactorily preferable because they need large amounts of addition due to their small mol absorption coefficient, it is difficult to adjust the main absorption to preferable areas, the masking effect is small due to low development activity, fogging is easy to occur while the development activity is high, stability on light, heat and humidity is low and magenta dyes created through the reaction of color developing agent are for short wavelength. It is the present status, therefore, that the performance is maintained with difficulty by combining some kinds of colored magenta couplers. Especially recently, employment of high speed fine grain silver halide emulsions and high color-developing magenta couplers has required colored magenta couplers to have higher performance.
Recently, in particular, it turned out that, when a color paper is printed from a color negative film, disparity occurs on hue of the finished color print due to the difference of the model of an instrument used for printing (hereinafter called a printer) and it became apparent that one of the causes was the image toner of color-developing dye obtained from colored magenta couplers used for a color negative film.
With regard to the fluctuation between printers, remarkable improvement are observed when using the colored magenta couplers described in Japanese Patent Application No. 122400/1990. However, they still are not on a satisfactory level.
In addition, together with change light-sensitive material for photographic use to small format and prevailing of panorama print (a picture is photographed at the central portion of 35 milli film oblongly and to print its photographed portion panoramically), photographic light-sensitive materials having high sharpness and high image quality are demanded.
On the other hand, it is known that some kinds of polymethine dyes are extremely effective as a means for spectrally sensitizing silver halide emulsions. For example, many types of compounds are described in pp. 194 to 234 of The Theory of the Photographic Process 4th edition written by T. H. James. For the above-mentioned sensitizing dyes, it is requested to satisfy the following conditions in addition to extending the area of light-sensitive wavelength of silver halide emulsion.
1) Spectral sensitization by means of dye sensitization is appropriate. PA0 2) Sensitization efficiency is so high that completely high sensitivity can be provided. PA0 3) The occurrence of fogging is not involved. PA0 4) There is no adverse interaction with other additives, for example, stabilizers, anti-foggants, couplers, DP' scavengers and coating aids. PA0 5) Desorption of dyes and the decrease of sensitivity are not caused when silver halide coating emulsions containing sensitizing dyes are left for a long time. PA0 6) Increase of fog density and decrease of sensitivity are not caused when silver halide light-sensitive materials containing sensitizing dyes are left for a long time under high temperature and high humidity. PA0 7) Added sensitizing dyes do not diffuse to the other light-sensitive layers to cause color contamination after development processing.
Various compounds have been proposed and synthesized in order to satisfy many conditions having important meaning when the above-mentioned silver halide emulsions are prepared. Among others, an azol ring trimethine cyanine dyes having a chalcogen atom inside the ring such as thiacarbocyanine, oxathiacarbocyanine, selenacarbocyanine and oxaselenacarbocyanine are known as main red sensitizers because they have preferable spectral in the red color area and they are excellent in spectral sensitization efficiency. Namely, for example, cyanine dyes substituting alkoxy groups described in U.S. Pat. No. 3,615,644 on the condensed ring, thiacarbocyanine dyes substituting methylenedioxy groups described in U.S. Pat. No. 2,429,574, thiacarbocyanine dyes substituting phenyl groups at 5th position described in U.S. Pat. No. 2,515,913, thiacarbocyanine dyes substituting carboxy groups at 5th position described in U.S. Pat. No. 2,647,050, thiacarbocyanine dyes substituted alkoxycarbonyl groups at 5th position described in U.S. Pat. Nos. 2,647,051 and 2,647,052, carbocyanine dyes substituted phenyl groups at 6th position described in U.S. Pat. No. 2,485,679, saturated carbon ring condensed thiazolocarbocyanine dyes described in U.S. Pat. No. 2,336,843, other carbocyanine dyes described in U.S. Pat. Nos. 1,846,302, 2,112,140 and 2,481,464, trimethine dyes having a substituent on a methine carbon atom described in U.S. Pat. Nos. 2,369,646, 2,385,815, 2,484,536, 2,415,927, 2,478,366, 2,739,964, 3,282,932 and 3,384,489 and trimethinecyanine dyes substituting anion groups described in U.S. Pat. Nos. 2,647,053, 2,521,705 and 2,072,908 and British Patent No. 654,690 and Japanese Patent Publication No. 21711/1961 are cited. Though some of the above-mentioned carbocyanine dyes are used singly and the others are used in combination with other plural dyes to obtain satisfactorily level, it has become apparent that contamination caused by the remaining of spectral sensitizing dyes in the light-sensitive materials after being subjected to development processing (hereinafter referred to as color-remaining contamination) is the factor of the above-mentioned fluctuation between printers. And, at that point, it has become apparent that conventional carbocyanine dyes are on the level that is extremely unsatisfactory.